Microwave-assisted Preparation of Copper Hydroxyphosphate and Characterization of Photocatalysis under Visible Light

doi:10.15541/jim20150413

Abstract

Abstract:

Copper hydroxyphosphate (Cu₂(OH)PO₄) was quickly synthesized by microwave-assisted method at low temperature (< 100℃) and normal atmosphere pressure, then characterized by XRD, SEM and Raman spectra. The synthesis parameters were investigated by a series of controled experiments. It is found that molar ratio, initial concentration of CuCl₂ and NaH₂PO₄, and surfactant species were crucial factors determining the formation and morphology of Cu₂(OH)PO₄. Cu₂(OH)PO₄ synthesized at different [PO₄^3-] (n(Cu)/n(P)=2) exhibited a various morphologies including grain-like, prism and long-prismatic. Addition of anionic surfactant and sodium dodecyl sulfate (SDS) greatly affects Cu₂(OH)PO₄ final morphology. The photocatalytic degradation of Cu₂(OH)PO₄ on methylene blue (MB) was evaluated with addition of H₂O₂ under visible light irradiation. The results showed that Cu₂(OH)PO₄ synthesized at conditions when n(Cu)/n(P)=2, [PO₄^3-]=0.0025 mol/L, 6.0 g urea and 0.10 g SDS, microwave heating at 80℃for 30 min exhibited best visible-light photo-degradation activity. The increase in HO· formation in the presence of Cu₂(OH)PO₄ and the inhibition of HO· generation by adding HO· scavengers (t-butanol) indicated that HO· generated in the reaction system was responsible for the enhanced MB decomposition. Cu₂(OH)PO₄ exhibited excellent stability and effectiveness after 5 consecutive runs in terms of photodegradation of MB.

Key words: copper hydrophosphate, microwave-assisted method, low temperature and normal pressure, photocatalysis

CLC Number:

TQ174

HU Xiao-Xia, ZHAO Lin, ZHAO Shu-Yu, LI Rong, XING Yan-Jun. Microwave-assisted Preparation of Copper Hydroxyphosphate and Characterization of Photocatalysis under Visible Light[J]. Journal of Inorganic Materials, 2016, 31(4): 421-426.

Figures/Tables 11

Fig. 1 XRD patterns of Cu2(OH)PO4 synthesized with different n(Cu)/n(P) (a) n(Cu)/n(P)=1; (b) n(Cu)/n(P)=2; (c) n(Cu)/n(P)=3; (d) n(Cu)/n(P)=4

Fig. 2 SEM images of Cu2(OH)PO4 synthesized with n(Cu)/n(P) at 1 (a), 2 (b), 3 (c), and 4 (d)

Fig. 3 Raman spectrum of Cu2(OH)PO4 synthesized with n(Cu)/n(P) at 2

Fig. 4 XRD patterns of Cu2(OH)PO4 synthesized with different [PO43-] concentrations (n(Cu)/n(P) =2) (a) 0.0025 mol/L; (b) 0.005 mol/L; (c) 0.010 mol/L; (d) 0.025 mol/L; (e) 0.100 mol/L

Fig. 5 SEM images of Cu2(OH)PO4 synthesized with different [PO43-] concentrations (n(Cu)/n(P) =2) (a) 0.0025 mol/L; (b) 0.005 mol/L; (c) 0.010 mol/L; (d) 0.025 mol/L; (e) 0.100 mol/L

Fig. 6 SEM images of Cu2(OH)PO4 synthesized without and with different surfactants (a) Without surfactant; (b) CTAB (CMC, 0.04 g); (c) PVP (m(PVP)/ [Cu2+]= 20, 0.64 g); (d) SDS (0.10 g)

Table 1 Influence of preparation conditions on the photocatalytic degradation of MB

Test	[PO₄^3-]/ (mol·L^-1)*	Temperature/℃	Time /min	Urea usage/g	SDS usage/g	Degradation efficiency /%
1	0.0025	80	30	6.0	0.10	52.91
2	0.0050	80	30	6.0	0.10	51.06
3	0.0100	80	30	6.0	0.10	47.30
4	0.0025	80	30	3.0	0.05	45.41
5	0.0025	80	30	6.0	0.05	50.79
6	0.0025	80	30	9.0	0.05	68.11
7	0.0025	70	30	6.0	0.10	44.19
8	0.0025	90	30	6.0	0.10	49.68
9	0.0025	95	30	6.0	0.10	60.08
10	0.0025	80	15	6.0	0.10	45.21
11	0.0025	80	60	6.0	0.10	51.61

Fig. 7 Surface photovoltage spectrum of Cu2(OH)PO4

Fig. 8 Possible mechanism in MB degradation by H2O2 over Cu2(OH)PO4 catalyst

Fig. 9 Reaction time dependence of emission intensity (excited at 300 nm and detected at 409 nm) a: Cu2(OH)PO4/H2O2-BA; b: H2O2-BA

Table 2 Degradation of MB in consecutive runs using the recycled Cu2(OH)PO4

Runs	Degradation efficiency/%
1	52.91
2	50.64
3	46.82
4	47.45
5	48.66

References 12

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